Preparation of halogenated fatty acid esters of cellulose



760 many of the commonly known esters of cellulose anhydrides andabasicorganic'catalyst are: 1

Patented Aug. 7, 1934 I I STATES P TENT OFFICE 1,969,468 I PREPARATIONOF HALOGENATED FATTY. H n g Aoin ESTERS 0 F CELLULQSE' Carl J. MalmandQharles'R. Fordyce, Rochester, v Y., assignors to EastmanKodakCompany,

Rochester, N. a corporation of New York i No Drawing; ApplicationOctoberf3; 1931,.

s ri No. 566,800 200laims. -(Cl.260 1ll1-) 1 This invention relatestothe chloracylation of are unsuitable. We have foundthat the'productcellulosic materials by means of a chloracyl chloof our process isfire-resistant which property is ride or anhydride in the presence of abasic, orcharacteristicof but'few of the esters of cellulose. ganiccatalyst. i r Our process compr'ses the chloracylation of cel-Heretofore in the esterification-ofcellulosic malulosic material such aspartially esterified esters terials in which chloracyl compounds havebeen of cellulose or. cellulose ethers containing free by? present, anon-basic catalyst has been employed droxyl groups by the use ofahalogenated fatty and the chloracyl compounds were merelyreacidchloride or anhydride and a basic organic garded as impellers orsolvents as they did not catalyst such aspyridine, cc-DlCOllIl,quinoline era 10 contribute any chloracyl groups tothe cellulose likebase, preferablydiluted with an organic solderivative formed vent.Cellulose such as'in the form of cotton It has been attempted to producecellulose de- 0r sulfite pulp may also be chloracylated by our rivativescontaining chloracyl groups by treatp s but he PI'OdHCtS formed-have notbeen ing organic cellulose esters having saturated acyl found to .be.asv val abl as th formed from 5 groups with chlorine or phosphoruspentachloe the chloracylation of partially esterified esters ride butthere are so many varying factors in that or ethers of cellulose. iprocess, such as temperature, duration of reaction, The followingexamples are for purposes of ilamount of illumination (in the case ofchlorine lustration andare not intended to' limit the scope sunlight hasbeen employed), catalysts, etc. that of our invention: J I 20 theresults which are to be obtained cannot be a Example I P P We have fmmdthat when 011107 ,About 50 lbs. of cellulose acetate having an rine 1Semployed to prepare cellulose chloracylates from organic esters ofcellulose containing acetyl content Qf 38% dlssglyed e mately 400 lbs.of ethylene chloride and 100 lbs.

saturated acyl groups that severe degradation of r 25 the cellulosemolecule occurs so that it appears igg g of chloracetyl chlonde nechloride is then added to break down Cenoblose or Y perhaps and themixture is maintained at a temperature sugars. The resulting productlacks in the qualof about approximately 10 hrs e ities necessary in acellulose derivative so that it a solid jeu s jobtamed' This 3611 f guhas apparently little if any value other thanas a a b c g a Chemlcalcurloslty- Also that process when dine may be dissolved in methylchloracetate and chlorine is employed as the chlorinating'agent, mustdepend on sunlight for the carrying out of 53 353 by prclPlta'tmg andwashing wlth mithyl the process, which dependence nullifies anycommercial value such aprocess might otherwisehave. a i V I It has alsobeen known to produce halogenated T Same Procedure 5 employed as inExamfatty acid esters of cellulose by first forming a ple I except thatchloracetic-anhydride is used ester of cellulose having an unsaturatedfatty Instead of chloracetyl omqn'de! acid group and then saturating thegroup with The products formed in the above examples are chlorine atoms.That pm'cess however obviously insolublein the usual-solvents such asacetone 40 cannot be employed when halogenated lower fatty etc.which'areemployed for the dissolving of the acid groups such aschloracetyl are to be attached a y esters of cellulose- HOWeVePi theyare to the cellulose soluble in the ,alkyl chloracetates which may be Wehave found a process of chloracylating celemmoyed alone mlxed i(11111911135 n he lulosic materials which is simple and easily conmaklngof Products t h duced ac- 15 trolled. We have found a process of formingcordmg oour lliVEDtlOIlJ' esters of celluldse containing a chloracylgroup The chloracetic esters of cellulose are especially in which theuse of sunlight or other dimcultly valuable for use for instance incinematographic controllable details are absent. We have found a methodof chloracylating cellulosic materials 5 by means of derivatives of thechlorinated fatty Example II sistance of these esters to the commonlyknown acids. We have found, contrary to general belief, that thehalogenated'fatty acid anhydrides composed oflartifician'l filaments Ican be employed to esterify cellulosic materials our process mayemployed for the produc 55 with P own groups and that theFeuulose @sterstion of esters .ofcellulose containing acyl groups containinghalogenated fatty ac1d groups D of either the halogenated higher fattyacids-or duced by u pr s a a u a s ta the halogenated lower fatty acids.Some of the to the action of most organic solvents, which esters whichca ibe. prepared by the u 0f adapts those esters for many purposes forwhich responding'rhalogenated fatty acid chlorides or base.

Cellulose acetate-chlorlaurate, cellulose acetate-bromstearate,lpellulose acetate chlorpropi onate, cellulose propionate-chlorbutyrate,cellulose ethyl ether-chloracetate, cellulose propionif it is desiredwhich will be attached to the cellulose will correspond to those in thechloracetyl compounds originally employed. Our invention contemplatesthe use of the halogenated fatty :acid anhydrides or chlorides generallyand it is to be understood that the fiuoro-bromoand 'iodo-compoundscor-'- responding to the chloro-compounds mentioned herein may beemployed although as the chlorocompounds are the more common and givegood results they willprobably be ordinarily employed. 5 The termcellulosic materials. as employed hereinIref'ers both to cellulose andto cellulose derivatives containingfree; hydroxyl groups availableforesterification.

wVarious obvious modifications such as the use of a halogenated fattyacid in conjunction with an unsubstituted fatty acid anhydride toesterify cellulosic material, and the like, also come within thecontemplation of our invention.

- We claim as our invention:

. r 1., A DI'QCGSS of preparing a cellulose derivative containing ahalogenated acyl group, which comprises treating cellulosicmaterial withan esterifying bath comprisinga compound selected from the groupconsisting of the anhydrides and the chlorides of the halogenated fattyacids in the presence of a tertiary organic base.

2. A process of preparing a cellulose derivative containing ahalogenated acyl group, which comprisestreating cellulosic material withan esterifying bath comprising a halogenated fatty acid anhydride inthepresence of a tertiary organic base. 3; IA proce'ssof preparing acellulose derivative containing a halogenated 'acyl'g'roumwhichcomprises treating cellulosic material with an esterifying bathcomprising a halogenated fatty acid chloride, in the presence ofatertiary-organic base. 4-.'-A=process of preparing acellulosederivative containing a halogenated acyl group which com-c prisestreating a cellulose; derivative containing freeland available hydroxyl'groups with an esteri', fying bath comprising a compound selected fromthe groupconsisti'ngzof the anhydrides and the chlorides'of 'thehalogenated fatty: acids inL-the presence of a tertiary organic base. Iv

' 5. A process of. preparing a cellulose derivative containing ahalogenated acyl group, which comprises treating a cellulose derivativecontaining freeand available hydroxyl groups with an esterifying bathcomprising a halogenated fatty acid anhydride in the presence of atertiary organic T 6.A process of preparing a cellulose derivativecontaining ahalogenated acyl group, which comprises treating a cellulosederivative containing free and available hydroxylgroups' with'an'esterihalogenated {fatty acid chloride in the presence of a tertiaryorganic base. 1'1. A processof preparing a-cellulo'se derivativecontaining ,a halogenated acyl group, which cornprises treatingfapartially esterified' cellulose ester withan esterifying bath comprisinga compound the cellulose.-

selected from the group consisting of. theanhydrides and the chloridesof the halogenated fatty acids in the presence of a tertiary organicbase.

8. A process of preparing a cellulose derivative containing ahalogenated acyl group, which comprises treating a partially esterifiedcellulose ester with an esterifying bath comprising a halogenated fattyacid anhydride in the presence of a tertiary organic base. I Y

9'. A process" of preparing a cellulose derivative containing ahalogenated acyl group, which comprises treating a partially esterifiedcellulose ester with an esterifying bath comprising a halogenated fattyvacid. chloride in the presence of a tertiary organic base.

10. A process'of' preparing a cellulose derivativecontaining ahalogenated acyl group which comprises treating cellulosic material withan esterifying bath containing a halogenated fatty acid compound in thepresence of a tertiary organic base.

11. A process of preparing a cellulose deriva-; tive containing achloracyl group which comprises treating cellulosic material with anesterifying bath comprising acompoundselected. from the group consistingof chloracetic anhydride and chloride, in the presence of a tertiaryorganic base.

12. The chloracylation of cellulosic material in the presence of acatalyst selected from the group consisting of pyridine, quinoline andtheir alkyl substituted derivatives. l p

13. A process of preparing a cellulose derivative containing ahalogenated fatty acid group which comprises treating a partially'esterified cellulose acetate with an esterifying bath containing ahalogenated fatty-acid compound in the presence of a tertiary organicbase. 14. A process of preparing a cellulosederivative containing ahalogenated fatty acid, group which comprises treating a cellulosederivative containing free and available hydroxyl groups with anesterifying bath containing a halogenated fatty acid, a. fatty acidanhydride and a tertiary organic base. 1

15.'A process of preparing a cellulose deriva-. tive containing .ahalogenated fatty acid group which comprises treating a partiallyesterifiedcellulose acetate with an esterifying bath compris ing ahalogenated fatty acid anhydride in the presence of a tertiary organicbase. v 1 v 16. A process of preparing 'a' cellulosederivag tive.containing a halogenatedfatty' acid group which comprises treating apartially esterified. cellulose acetate with an esterifying bathcomrising a halogenated fatty acid chloride inthe presence of a tertiaryorganic base. I v, r;

17. A process .of preparing a cellulose acetatechloracctate whichcomprises treating a partially esterified cellulose acetate with anesterifying bath comprising chloracetic anhydride in the presence of atertiary organic base. '18. A process of preparing a celluloseacetatechloracetate which comprises treating a partially esterifiedcellulose acetate with an esterifying bath comprising chloraceticchloride-in the pres ence of a tertiary organic base.

19. The chloracylation of a partially esterified cellulose ester in thepresence of a catalyst selected from the. group consisting of pyridine,quinoline and their alkyl substituted derivatives.

'20. The chloracylation of a cellulosic material in the presenceof'pyridine as'the catalyst;

. CARL J. MALM. x CHARLES R. 'FORDYCE.

